30692-16-1Relevant academic research and scientific papers
Continuous flow synthesis of ketones from carbon dioxide and organolithium or grignard reagents
Wu, Jie,Yang, Xiaoqing,He, Zhi,Mao, Xianwen,Hatton, T. Alan,Jamison, Timothy F.
supporting information, p. 8416 - 8420 (2014/08/18)
We describe an efficient continuous flow synthesis of ketones from CO 2 and organolithium or Grignard reagents that exhibits significant advantages over conventional batch conditions in suppressing undesired symmetric ketone and tertiary alcohol byproducts. We observed an unprecedented solvent-dependence of the organolithium reactivity, the key factor in governing selectivity during the flow process. A facile, telescoped three-step-one-flow process for the preparation of ketones in a modular fashion through the in-line generation of organometallic reagents is also established.
Catalytic ketonisation over oxide catalysts. Part IX. Single step synthesis of aliphatic saturated and unsaturated C11 - C 13 ketones from carboxylic acids
Glinski,Gibka
, p. 299 - 302 (2007/10/03)
Metameric undecan-x-ones (x = 2-6), dodecan-y-ones (y = 2-5), tridecan-z-ones (z = 4-7) and two unsaturated aliphatic ketones were prepared by vapor phase ketonisation of the appropriate monocarboxylic acids in the presence of 20 wt% MnO2/Al2O3 catalyst under flow conditions. The ketones were obtained in yields between 48 and 89% in a multigram scale (80-250 g). Their physical and spectral data have been determined.
Catalytic ketonisation over oxide catalysts. Part VII. Ketonisation and cross-ketonisation of aliphatic esters over CeO2 and ZrO2 supported on alumina
Glinski,Szymanski,Lomot
, p. 1033 - 1038 (2007/10/03)
Catalysts of general formula xwt% MO2/Al2O 3, where x = 10, 20 or 30 and M = Ce or Zr have been studied in the ketonisation and cross-ketonisation of aliphatic esters under flow conditions between 548-723 K. Ketonisation of ethyl pentanoate, heptanoate and nonanoate has led to nonan-5-one, tridecan-7-one and heptadecan-9-one, respectively. The conversion of esters increased with temperature and at 698 K a quantitative conversion was observed, irrespective of the type of ester used. A maximum yield of ketone (46% for nonan-5-one, 60% for tridecan-7-one and 50% for heptadecan-9-one) was observed at 673 K. As a result of the cross-ketonisation of a mixture of ethyl pentanoate and ethyl nonanoate (3:1 molar ratio), three ketones were formed: nonan-5-one, tridecan-5-one and heptadecan-9-one. At 698 K, maximum yields of ketones were noted (37, 46 and 8%, respectively) together with a 90% conversion of esters. The catalysts were characterized by XRD, TPR and surface area measurements.
Nickel-catalyzed cross-coupling between functionalized primary or secondary alkylzinc halides and primary alkyl halides
Jensen, Anne Eeg,Knochel, Paul
, p. 79 - 85 (2007/10/03)
In the presence of Bu4NI (3 equiv) and 4-fluorostyrene (20 mol %), unreactive primary and secondary alkylzinc iodides undergo nickel-catalyzed cross-couplings with various primary alkyl iodides or bromides. More reactive secondary dialkylzincs and the mixed zinc organometallics RZnTMSM undergo the cross-coupling reaction in the absence of Bu4NI. The bicyclic secondary diorganozinc 6 prepared via boron-zinc exchange reacts with high retention of configuration. Free NH-groups are tolerated in the cross-coupling allowing the synthesis of aminated products.
The radical-chain addition of aldehydes to alkenes by the use of N-hydroxyphthalimide (NHPI) as a polarity-reversal catalyst
Tsujimoto,Iwahama,Sakaguchi,Ishii
, p. 2352 - 2353 (2007/10/03)
Hydroacylation of simple alkenes with aldehydes via a radical process was successfully achieved by the use of N-hydroxyphthalimide (NHPI) as a polarity-reversal catalyst. Thus, 5-tridecanone was obtained by the reaction of oct-1-ene with pentanal in the presence of small amounts of NHPI and dibenzoyl peroxide (BPO).
New efficient nickel-catalyzed cross-coupling reaction between two Csp3 centers
Giovannini,Strudemann,Devasagayaraj,Dussin,Knochel
, p. 3544 - 3553 (2007/10/03)
The presence of a remote unsaturation (double bond, carbonyl group, cyano group) in an alkyl halide facilitates its cross-coupling reaction with various diorganozincs in the presence of Ni(acac)2 (7.5-10 mol % in THF/NMP mixtures). These results were used to develop a new general cross-coupling reaction between functionalized diorganozincs and alkyl iodides using m- or p-trifluoromethylstyrene as a reaction promotor and Ni(acac)2 as a catalyst (7.5-10 mol %; -35 °C, 5-10 h) leading to a broad range of polyfunctional cross-coupling products.
An efficient nickel-catalyzed cross-coupling between sp3 carbon centers
Giovannini, Riccardo,Stüdemann, Thomas,Dussin, Gaelle,Knochel, Paul
, p. 2387 - 2390 (2007/10/03)
Since the pioneering work of Wurtz, cross-couplings between sp3 carbon centers have had the reputation of being difficult. In the presence of a catalytic amount of m-trifluoromethylstyrene, an efficient cross-coupling reaction takes place between polyfunctional primary alkyl iodides and diorganozinc compounds [Eq. (a)] to give a general catalytic cross-coupling between sp3 carbon centers. Piv = pivaloyl; Pent = pentyl; acac = acetalacetonate; NMP = N-methylpyrrolidone.
